Seriesand the preparation



applieation'serial N0. "298,182, filed iily 1 0, 1-9

United States Patent C) "ice 7 159,935 (339B SERIESAND THE PREPARATION rain catheterana Peter, mating-eh; fsiiifierlnnd, fignors to Sandoz A. G., Basel, Switzerland, a Swiss No Drawing. Applicatibnaltgny l, 1953,

Serial :No. 352,96 Claims priority, application Switzerland May a, 1952 12 Claims. cream-272 The present invention relates to dyestuffs of the aza(3)- benzanthrone series andao the preparation thereof.

, This application is a continuation-in-part of copending isclosing inter alia compounds of the antlir'zn'ayridirie which correspond to :the formula wherein v stand "for chlorine, Breanne, intro or 'merhex and w stands for hydrogen, chlorine, (bromine, lower alkyl or the sulfonic acid group. p

These compounds can be prepared by condensing primary amines of the anthraquinone series, corresponding- 7 to the formula wherein v and w haverthe aforementioned significances, with l ower .alkyl ,esters of acetoacetic acid under acid conditions i an 'orgariic so'ivent and while distillir'ig' otr 'th b rqdncts formed durin rnereaefion.

he present invention is "concerned witli valiiabie ayei we.

.32 wherein z standsf oihydrogen, chlorine, bromine, methyl, lower alkoxy, mononuclear aryloxy or SOaH, R1 stands for hydrogen, alkyl or-.acyl,.,R2' stands for hydrogen, alkyl, cycloalkyl, aralkyl, aryl or etthe residue of an azo compound, and n is one of the integers 1, 2, 3 and 4.

. he..-new dyestufis of the fi fiBX-benzanthmug, series wherein 2 stands forahy drogen,chloriue hmmlnegfil or SOaH, can be obtained by condensing", in'theprestice 2,759,939 Patented Aug. 21, .1956

aza 3 benzanthrones which w ereas stands for hydrogen, chlorine, :larotriine, methyl and SQB'H, and -w stands ,for chlorine, bromine or nitro, ammonia or substituted ammonia derivatives-posisessii'rg least one replaceable hydrogen atom linledto the nitrogen -atom, and-if deSiIed by't'reating the thusobtained products withgsulfonating agents and/orwhen the v adicals of the substituted ammonia derivatives are 0 Jsapofiiiiablewith,saponifyiug agents.

7111 the condensation, the negative substituent in the 6 sition of the aza(3j) '-ben'zanthrone is replaced by an am 0 radical. The negatively substituted azaf('3 )*benz'aiithrones which are employed as starting materials for the present invention can be prepared according to the of the aforesaid copendinglapplication Serial jThus, for example, .1-carbethoxy=2 rnethy1-'6- v {(3')-benZaiitlrrone-4-S1ilionic acid may ,b'e pred by con'den.sing..1-trt1ino-4 bromoarithraguinoneqlforiic acid with acetoacetic acid ethyl ester under acid conditions in an organic solvent, such as ben'zene or'th'e like. Also those of the new dyestufis of the aza'('3-) benzanthrone series which correspond to the above-mentioned formula, but wherein z stands ,fQI'JlQWQI alkoxy and mononuclear aryloxy, are obtained according to the process of copending application Ser. No. 298,182.

Suitable substitlllipn piqdl ctspf ammonia for use in the condensation according to the present invention comprise for example acid amides such as;acetamide, I-methyl- 40 benzene-4-sulfonic acid amide, etc., secondary amines such as methylaminohenzene, etc., and especially primary amines, which maybe of the aliphatic, cycloaliphatic, 'af'ro'iiiatic or hete'rocyclicsefies'. Thus, use 'm'ay b e "made inter alia cf =aiiiylam'ine, cyclohertylairiine, be'n'zylaniine, amin'obe'iiz'ehe, the amino-meth'ylbenzenes, :the aminomethoxybenzenes, the aminorchlorobenzenes, 1-amino-4- nitrobenz ene, 1 aminobenzene-4-sulfonic acid, 2-amino-1,- 1 df'h'enyl, t "rriino lfl diphenyl, 4,"4diamino-l;-1'-diphenyl, afi' diamino-l,l=diphenyl sulfone, 4,4diai nino- 1,11' diphenyl ilfl' slilfone, 4-amino-ilgl' --azo ben'zene, the more complicated azo dyestuffs, -4-aminopyr'idine, etc.,',to name a few of themore representative substitution prodnets.

In the condensation, the components v.are heated together as such or in a solvent such as water, dioXane,

'ethylalcohol, butyl alcohol, cycloheiranol ph'enol, methoxy-benzene, 1,2,3,4-tetrahydronaphthalene, chlorbbenzene, nitrobenzene, dimethylaminobenzene, and with the addition of an acid-binding agent, suchmfonexample as sodium acetate, potassium acetate, sodium carbonate, po-

tassium carbonate or the like. The addition of copper or copper salts, which is conventional and necessary in similar condensations in 'the anthraguinone series, is surprisingly unnecessary in the condensation according to 5 the present invention and in some cases may even be prejudicial. In view of the ready course of the reactions, low temperat'uresfor example 40 to 130are sulficie nt .even with such weakly basic aminesas l-amino-4- nz'ep r 4,4-diarnino-"l ;1".-diphjenyls 1fone, the con ensa'tion' of which with compounds of the anthraquinoiie'. series ,is' exceedingly troublesome. I

"The condensation products, according to 'theinve'ntion,

are isolated from the reaction mixture by salting out from the aqueous solution or by dilution of the ingredients in organic solvents with alcohol, followed by filtering, washing and drying. The products are yellow to red powders which dissolve with like colorotion in water in so far as they contain a sulfonic acid group, and are otherwise readily to diflicultly soluble in organic solvents, the resulting solutions being similarly colored.

Those products which contain no sulfonic acid groups are useful as pigments for coloring lacquers, printing pastes, paper, etc., and for coloring synthetic fibers in the spinning process. They can be converted into watersoluble sulfonic acids by treatment with fuming sulfuric acid. The water-soluble sulfonated products are suitable for dyeing fibers of all types, e. g. cotton, wool, silk, synthetic polyamide fibers, polyvinyl fibers, etc.

The following examples set forth representative presently-preferred embodiments of the invention; these examples are intended to be illustrative and not limitative of the invention. The parts and percentages are by weight; the temperatures are in degrees centigrade.

EXAMPLE 1 24 parts of 1-carbethoxy-2-methyl6-bromo-aza(3)- benzanthrone-4-sulfonic acid, 100 parts of water and 150 parts of aqueous ammonium hydroxide solution of 30% strength are gradually heated to 75 in the course of 6 hours while stirring, and then maintained for 2 more hours at this temperature. dium chloride are added to the reaction mass. The latter is allowed to cool to 50, and the formed precipitate separated by suction filtration, washed with aqueous sodium chloride solution of strength until the wash water is only weakly colored, and dried. The thus-prepared prodnot is an orange-yellow powder which corresponds to the formula $1) CH: HsCaO-C and dissolves with yellow coloration in water. The resultant solution exhibits a yellow-green fluorescence. The dyestuff thus obtained dyes wool and Dynel yellow.

EXAMPLE 2 NH-SOy-O-CH:

is filtered off with suction at 55. The precipitate is washed with ethyl alcohol and hot water and dried. 12 parts of the thus-obtained orange-yellow product are added, at 2530 and with stirring, to 25 parts of sul- Thereupon 10 parts of so- I furic acid (92% strength), and maintained at 30-35 for 3 hours. Then 8 parts of water are added dropwise to the solution at 25-30; the resultant precipitate is filtered OE and washed with sulfuric acid (70% strength). The acid filter cake is then stirred into a mixture of 250 parts of water and 30 parts of aqueous sodium hydroxide solution (30% strength), and stirring is continued for 4 hours. The produced dyestutf is suction-filtered otf, washed neutral with water, and dried. It is thus obtained as a citron-yellow powder which corresponds to the formula ll 0 N H:

and dissolves in benzene with yellow coloration and with strong yellow-green fluorescence.

EXAMPLE 3 24 parts of 1-carbethoxy-2-methyl-6-brorno-aza(3)- benzanthrone-4-sulfonic acid, 10 parts of sodium carbonate, 6 parts of benzoic acid amide and 200 parts of water are stirred together for 3 hours at 95. The solution is then gradually run into 500 parts of water and 25 parts of hydrochloric acid (30% strength) at 20 while stirring, and the resultant precipitate is suction-filtered ofi, washed neutral with aqueous sodium chloride solution (10% strength) and dried. The obtained orangebrown powder, corresponding to the formula SOIH dissolves with yellow-orange coloration in water.

EXAMPLE 4 and dissolves in organic solvents, such as alcohol, benzene, ethyl acetate and benzine, with yellow coloration and with strong yellowish fluorescence.

meltat 1 92-194" and dissolve in benzene with yellow coloration and yellow-green" fluorescence.

EXAMPLE 6' 24 parts of 1-carbethoxy-2-methyl-6-bromo dza(3 benzanthrone-4-sulfonic acid, 12 partsof sodium carbonate, 5.3 parts of cyclohexylamine and 250 parts of water" are stirred together at 90-95" for 7 hours. A I

precipitate forms This precipitate is filtered off with suction at roomtemperature (20 30"), washed with aqueous sodium chloride solution" (2% strength) until the filtrate (wash water) is only weakly colored, and dried. The thiis-obtained yellow powder corresponds to the formula HsCaO- and dissolves with yellow coloration in water. It dyes wool orange-yellow.

EXAMPLE 7 24 parts of 1-carbethoxy-Z-methyLG-bromo-azafi)- benzanthrone-4-sulfonic acid, 6 parts of Z-aminopyridine, parts of potassium carbonate and 250 parts of water are stirred together at 95 for 10 hours. Thereupon; the reaction solution is stirred into 600 parts of hydrochloric acid (10% strength) at 90. After cooling the resultant mixture to the precipitate which separates is filtered ofi with suction, washed with cold water, and triturated with such quantity of sodium carbonate as is necessary to convert the dyestuff acid into the sodium salt. The thus-obtained dyestulf, after drying, is an orange powder which corresponds to the formula and dissolves in Water with yellow-orange coloration; It dyes wool orange.

p 6 EXAMPLE 8 40 parts of l carbethoxy 2,4 dimethyl 6- bromo azafi)-benzanthrone, 10 parts of aminobenzeiie; 20' parts of anhydrous potassium acetate and 60 parts of hydroxyhenzene are stirred together at until a test specimen of the reaction mixture-taken up in ethyl ailcoliol; filtered" and washed with hot water'is halogenfrejej'. The reaction mass is then allowed to cool to 75f, 200 parts of ethyl? alcohol are added dropwise, and the resultant precipitate suction-filtered off at] 50 The precipitate isw'ash'ed with ethyl-alcohol untilthe wash Water is only weakly colored, after which it is washed with'liot Water" and then dried. The so-obtaine'd dy'efstuff ease consists of fine orange needles which melt'at 185-186.

14 parts of the thus-prepared base are stirred into'29 parts of sulfuric acid monohydrate. The resultant solution is heated to 40 until a test specimen, neutralized with sodium hydroxide, is completely soluble in water. Thereupon the reaction mass is stirred into 1000 parts of Water, to which 200 parts of sodium chloride and 200 parts of aqueous sodium hydroxide solution (30% strength) have been added, and the resultant precipitate is then filtered oil with suction. The precipitate is washed with aqueous sodium chloride solution (5% strength) and dried. The thus-obtained dyestufi dyes Wool orange-yellow. It corresponds to the formula;

, sonar EXAMPLE- 9 20.5 parts of l-carbethoxy-2,4-dimethyl-6-bromo-aza- (3)-benzanthrone, 16' partsof l-aminobenzene-4-sulfonic acid,-20 parts of potassium. acetate, 50 parts of'hydroxybenzene and 50' parts of water are stirred together atll0-= until a test specimen is completely Water-solublel 100 parts of water and 210 parts of sodium chloride are then added to the reaction mass, the hydroxybenzeneis distilled off withstearrnthe remaining mixture allowed to cool to 30, and the resultant precipitate filtered off with suction. This precipitate is then washed with aqueous sodiumchloride solution (2% strength) and dried. The product is a dyestuif with properties similar tothat obtained according to Example 8. It corresponds to formula 1 o NIH-0801B;

EXAMPLE- 10 40 parts of 1-carbomethoxy-2,4-dimethyl-6-bromo-aia- (3)-benzanthrone, 22 parts of 2-amino-1,l-diphenyl, 20 parts of anhydrous potassium acetate and 150 parts of m butyl alcohol are stirred together at until a test specimen-taken up in ethyl alcohol, filtered and: washed with ethyl alcohol and hot water-is halogen-free. The

reaction mixture is thereupon allowed to cool to room temperature (2030), and the formed precipitate is filtered ofl? with suction. The precipitate is then washed with methylalcohol until the wash water is only slightly colored whereupon it is washed with water and then dried. The so-obtained dyestufif base dissolves with orange-yellow coloration in chlorobenzene.

I 44 parts of the dyestufi base are added, with stirring, to 240 parts of sulfuric acid monohydrate and the mixture isheated to 30-35 until a test specimen, neutralized with sodium hydroxide, is completely soluble in water. The solution is then poured into 2000 parts of water, the resultant precipitate is filtered off with suction, and washed with aqueous sodium chloride solution (2% strength) until the wash water runs neutral. The moist precipitate is triturated with a suflicient quantity of sodium carbonate to convert the dyestufl? acid into the sodium salt, after which it is dried. The resultant dyestul'l dyes wool orange. It corresponds to the formula SOaH ll NH If, in the present example, the 40 parts of l-carbomethoxy-2,4-dimethyl-6-bromo-aza(3)-benzanthrone are replaced by 41 parts of 1-carbethoxy-2,4-dimethyl-6-bromoaza(3)-benzanthrone, and the 22 parts of 2-arnino-1,1- diphenyl are replaced by 22 parts of 4-amino-1,1-azobenzene, and the procedure of the example otherwise ad hered to, there is obtained a product which dyes wool in red shades.

EXAMPLE ll 41 parts of 1-carbethoxy-2,4-dimethyl-6-bromo-aza(3)- benzanthrone, 21 parts of 1-amino-3-nitrobenzene, 20 parts of anhydrous potassium acetate and 150 parts of nitrobenzene are stirred together at 120 until a test specimentaken up in ethyl alcohol, filtered, and Washed with ethyl alcohol and hot wateris halogen-free. The reaction mass is then allowed to cool to 30, diluted with 50 parts of ethyl alcohol and the resultant crystalline precipitate filtered oil with suction, washed with ethyl alcohol, then Washed with hot water, and dried.

parts of the thus-prepared dyestuft bases are stirred into 22 parts of sulfuric acid monohydrate and 11 parts of fuming sulfuric acid (28%), and the mixture heated produced dyestuff dyes wool orange-yellow. It corresponds to the formula (II) (EH: 5C:O-C\ C f N I BOaH EXAMPLE 12 84 parts of 1-carbomethoxy-2,4-dimethyl-6-bromoaza(3)-henzanthrone, 27 parts of 4,4-diamino-l,1'-diphenyl-2,2'-sulfone, 40 parts of potassium acetate and 800 parts of n-butylalcohol are stirred together at 120 until a test specimen-taken up in ethylalcohol, filtered and washed with hot wateris halogen-free. The reaction mixture is then allowed to cool to 20, and the resultant precipitate is filtered off with suction, washed with methyl alcohol and then with hot water, and dried. There is thus-obtained a red pigment which corresponds to the formula EXAMPLE 13 12 parts of l-carbethoxy-2-methyl-6-bromo-aza(3)-benzanthrone-4-sulfonic acid, 25 parts of the aminodiazo compound of the formula SO;Na

to 50-55 until a test specimen, neutralized with sodium hydroxide, is completely soluble in water. is then stirred in 1000 parts of water and the resultant precipitate suction filtered off, washed with water until the wash water runs neutral, the moist precipitate triturated with sufiicient sodium carbonate to convert the dye- The solution stirred together for 24 hours at 90.

6 parts of sodium carbonate and 200 parts of water are 20 parts of sodium chloride are then added to the reaction mass and the resultant precipitate is filtered off with suction. The precipitate is taken up in 1000 parts of Water to which 50 parts of ethylalcohol have been added and the mixture is stufi acid into the sodium salt, and then dried. The thusheated to while stirring, then 200 parts of sodium chloride are added to the" mixture and the resultant precipitate is filtered OE With suction at 80 The filter precipitate is then washed with aqueous sodium chloride solution with strength after which it is dried. The

dyestuif which corresponds to the formula 5 O CH: HlCaO-tl'l and melts at 193-196. They dissolve in pure sulfuric acid with red coloration which, upon the addition of para formaldehyde, turns toward the violet.

CH1 8 OI dissolves with red-orange coloration in water and dyes cotton orange from a bath containing sodium sulphate.

EXAMPLE 14 24 parts. of 1-carhethoxy-2-methyl 4,6-dibro1noaza;(3)'- benzanthrone, 9 parts of1-amino-4-acetylaminobenzene, 19/ parts oftpotassiutn' acetate and 150 partsof n-butylalcoholare'stirredxat' 100 for 5 hours; 100 parts ofethylalcoholzand lOO'pai-ts of water are then added to the mass 5 and, after the latter has cooled to 45, the formed: precipitate is filtered off with suction. This precipitate is washed with ethylalcohol until the wash water runs colorless after which it is washed with water, and then dried. 10. parts of the so-obtained orange powder, 15 parts by volume of aqueous potassium sulfide solution of 50% strength and 30 parts of hydroxybenzene are heated together an an. autoclave to 120 for 16 hours. Thereupon the hydroxybenzene is removed by steam distillation, the remaining solution filtered, the filtrate rendered alkaline with sodium carbonate at 95, and 5 parts of sodium chlorideadded per 100 parts by volume ofsolution, while stirring. The resultant precipitate is filtered off with suction and Washed with hot aqueous sodium chloride solution of. 5% strength until the filtrate runs colorless and nolonger has an alkaline-reaction. Upon drying-the precipitate, there is obtained a red dyestulf powder which corresponds to the formula EXAMPLE 16 i) r mO-Nm and dissolves with red coloration in hydrochloric acid' of 10% strength.

EXAMPLE 17 19 parts of l-carbethoxy-2,4-dimethyl-6-chloro-aza(3)- benzanthrone, 5 parts of 4,4-'-diamino-l=,l-diphenyl,- 20 parts of. potassium acetate and 40 parts of hydroxylienzone are stirred together at 1l5- untila test specimen--- taken up in ethylalcohol,. filtered. and. washed with hot water-45 halogen-free. The reaction mixture is then cooledwto parts of ethylalcohol are added, and the resultant precipitate is filtered off with. suction at 20 The. precipitate is washed with ethylalcohol until the waterruns colorless, after which it is washed with hot.

water .andfi's finally dried. There is thus obtained'a brownredipowder which corresponds to the formula and which dissolves with orange-red colorationi in chlorobenzene.

EXAMPLE" 1'8' 24-parts of l-carbethoxyQ-methyl-6-brorno'aza( 3 )-ben-' zanthrone-4-sulfonic" acid, 5.5 parts of methylaminobem zen'e', l0parts of sodium carbonate and 250mm of water are stirred at 75-80 for' 4 hours. The resultant'precipitate isfilter'ed off with suction at 20, washed with aqueous sodium chloride solution of 10% strength until the filtrate (wash water) runs neutral, after which it is dried. The thus obtained dyestulf dissolves with red coloration in water and dyes wool Bordeaux red.

the formula 47 parts of 1-carbomethoxy-2-rnethyl-4,6-dibrorno-aza- (3)-benzanthrone, 23 parts of l-aminoanthraquinone, 12 parts of anhydrous potassium acetate, 200 parts of chlorobenzene and 0.3 part of copper powder are stirred together The reaction mass is then allowed to cool and after diluting with chlorobenzene the resultant precipitate is filtered oil with suction. is washed with chlorobenzene, then with methylalcohol 25 at 125 for 100 hours.

EXAMPLE 19 It corresponds to The precipitate obtained pigment corresponds to the formula and thereupon with water, and is finally dried. The soprocess and for pigment printin set forth in tabular form in the following agent, it can be used for coloring viscose in the spinning Further representative dyestufis according to the present invention which can be prepared in manner analogous to the procedure set forth in the foregoing examples, are

Table Color of Solu- Example Aza(3)-benzanthrone Substitution Product of Ammonia tion of Con- No, (1 e n s a t i o 11 Product 20 1 earbopropoxy 2,4 dimethyl 6 1-amino-2,3-dimethylb PM orange in bromo aza (3)-benzanthrone. chlorobenzene. Lamina-2,4-diemthylbenzene. Do. l-amino-2,fi-dimethylbenzene. Do. PaminmllA-dlmfithflbfllllfifle orange-yellow in chlorobenzene. 1-am1no-3,5-dimethy1benzene orange in chlorobenzene. 25 1 carbomethoxy 2,4- dimethyl -6 1-amino-2,6-dimethylbenzene ornage-yellow bromo-aza (3)-benzantl1rone. in chlorobenzene. 1-amino-2,4,fi-trlmethylbenzene l-amino-Z-ethylbpmenn orange in chlorobenzene. l-amino-Z-chlorobenzene Do. 1-amino-3-cblorobenzene. Do. 1-amino-4-chlorobenzene Do. dehydrothio red in chlorobenzene. 32 1-carbeth0xy-2,4-dimethyl-6br0m0- 1-amino-2-methy1benzene orange n aza(3)-benzanthrone. chlorobenzene.

1-amino-3-methylbenzene D 1-amino-4-rnethybenzene. Do.

l-amino-Z-methoxybenzene D I-amino-Z-methoxy-fi-meth ylbenzene Do.

1-amino-4-phenoxybenzene Do.

1-ami11o-4-phenylhenzene D 1-aminonaptl1alcne Do.

1 carbomethoxy 2 methyl 4,6 -dil-amino-G-chloroanthraquinonc red in nitrobromo-aza.(3)-benzanthrone. benzene. d 1-amino-7-chloroanthraquinone Do.

1-ami.no-6,7-dichloroanthraquinone- Do. Lamina-5,6,7,8-tetrahydronaphthalene orange in chlorobenzene.

46 do 2-amino-5,6,7,8-tetrahydronaphthalene Do.

47 dn methylenune orange-yellow in chlorobenzone.

48 dn octylm'nirm Do 49 1-carbethoxy-2,4-dimethyl-6-brom0- dimethyl m orange in chloaza(3)-benzanthrone. robenzene. 5n dn ethylarninnhnnvpnn d i hl benzene. -do acetylaminebenzene yellow-orange in chlorobenzene. do butyrylaminobenzene D do benzoylarninobenzene Do. do 4-methylbenzoylaminobenzene Do. do 3-chlorobenzoylarninobenzene Do. 1-carbethoxy-2-methyl-6-bromo-azal-arninobenzene-Z-carboxylic acid red in water.

(3)-benzanthrone-4-sultonie acid.

57 do l-aminobenzene-3-carboxylic avid Do. l-aminobenzene-i-carboxylic avid Do. 4,4-diaminostilbene-2,2-d1sulfonic arid Do.

dehydrothiotoluidine-sulfonic acid Do.

4-(4-ami.uo)-benzoy1amino-1,1-azobenzene-3-carboxylic acid, orange in water.

Tabla-Continued Color of Solu- Example Aza(3)-benzanthrone- Substitution Product of Ammonia tion 01' C011- No. 6. e n s a t l o 11 Product 62 do 4-hydro:y-4!-(4"-amino)-benzoylamtno-1,1'-azobenzene 3;carboxylic acid Do.

' OH: H 0 0 OH 63 do H|N-N= QED-NH red in water.

OxH

OH. /JJ=O.-N=NQS 0 :H 64 dn HiN CH=CH N I Do.

N=C 0 1H H O s 65 do 2-an11no-5-hydroxy-6- (2.'-carboxybenzene-l!)-azonaphthalene-7,4 -disulion1c. Do.

ac 66 1-carbomethoxy-2,4-dimethyl-6-bromoethanolamine orange-yellow aza(3)-benzanthrone. in chlorobenzone.

EXAMPLE 67' 21 parts of 1-amino-2-phenoxy-4-(4-methyl)-phenylamino-anthraquinone, 40-parts of acetoacetic acid ethyl ester, 40 parts of chlorobenzene and 3 parts of l-methylbenzene-4-sulfonic acid are heated to 115 while stirring. Readily-volatile reaction products are removed from the reaction zone by entrainment in, a gentle. stream of air passed over the reaction vessel. The temperature is gradually raised to 125. As soon as a test specimen of the reaction mixture turns yellow in benzene and there is no further change in this color, the mixture is allowed to cool to 80, 150 parts of ethyl alcohol are added in the course of 20 minutes, and the mixture allowed to cool further to 20. The resultant base which crystallizes out is separated by suction filtration, and then washed with ethyl alcohol until the wash-liquid runsweakly yellow in color, after which it is washed with water and then dried. The base is an orange powder which dissolves with yelloworange coloration in benzene.

parts of the base are introduced at 0 into a mixture of 75 parts of sulfuric acid monohydrate and 25 parts of fuming sulfuric acid of 28% strength. As soon as a test specimen of the reaction mixture, after neutralization of the specimen with sodium hydroxide, has become completely water-soluble, the reaction mass is introduced into 500 parts of an aqueous sodium chloride solution of 25% strength, the temperature rising to 50. After cooling back to 20, the precipitate is suction-filtered oif and washed neutral with aqueous sodium chloride solution of 25% strength. The moist filter cake. is pasted up with sodium carbonate and is then. dried. There is thus obtained a dyestuif in the form of a brown powder which dissolves with orange coloration in water and dyes wool orange from an :acid bath.

EXAMPLE 68 25 parts of 1-amino-2-(4'-tert.-amyl)-phenoxy-4-phenylamino-anthraquinone, 40 parts of acetoacetic acid ethyl ester, 40 parts of chlorobenzene and 3 parts of l-methylbenzene-4-sulfonic acid are heated to 130 while stirring, a gentle stream of air being passed over the reaction mixture to remove easily-volatile reaction products. The temperature of 130 is maintained until a test specimen of the reaction mixture turns orange-yellow in benzene and there is no further change in this color. After cooling the reaction mixture to 80, 0 parts of ethyl alcohol are then added in the course of 30 minutes, after which the mixture is allowed to cool down to The formed precipitate is filtered ofi'with suction and washed with ethyl alcohol until the wash-liquid runs only weakly yellow in color, after which the washing is completed with. water. The resultant base is, in dry form, an orange powder which dissolves with orange-yellow coloration in benzene.

10 parts of the said base. are introduced at 0 into a mixture of 75 parts of sulfuric acid monohydrate and 25 parts. of fuming sulfuric acid of 28% strength, the mixture being. stirred at 03 until a test. specimen thereof, after neutraliaztion with sodium hydroxide, is completely soluble in water. The reaction solution is then introduced into 500 parts of'a'queoussodium' chlorideso'lution of 10% strength and then filtered oif with suction. The precipitate is washed with 10% aqueous sodium chloride solution andithen taken up in 500'parts of" water, warmed to 3 parts of sodium carbonate are added and the dyestufi' is precipitated at by the gradual addition of'100'parts of sodium chloride. The" crystalline precipitate is filtered off with suction while hotv and is washed with hot 20% aqueous sodium chloride solution until the wash-liquidruns oif colorless; Thethus-obt'ained dyestutf'is, in the dry state, an orange crystalline powder and dissolves with orange-yellow coloration in water. It dyes wool orange-yellow from an acid bath.

EXAMPLE 69 If, instead of 2 1 parts of 1amino-2'-phenoxy-4-(4"- methyl)-phenylamino-anthraquinone, there are used in Example 67, 18 parts of l-amino-Z-methoxy-4-(4-methyl)-phenylamino-anthraquinone or 19 parts of l-amino- 2-propoxy-4-(4"- methyl) 4 phenylamino anthraquinone, similar dyestufis are obtained, dissolving with orange coloration in water and dyeing wool orange from acid baths;

EXAMPLE 70 Adye-bath is prepared from: 13 part of. the: dyestuft according to Example 1,. 6000 parts of' distilled water, 10 parts of anhydrous sodium sulfate: and 1.5 parts: of acetic acid and 100 parts of wool are. entered at 5.060.. The bath. is heated to boiling in the' course: of 30 minutes. After boiling for a half hour, 1.5 partsof acetic; acid (100%) are again added to the. bath and boiling continued for an additionalhalf'fhour. The dyed giattzlrial is then withdrawn. from the bath, washed and I'le The other hereinbefore-disclosed dyestuffs may be used for dyeing in essentially similar manner.

EXAMPLE 7 1" 100 parts of an aqueous; paste (of 20% strength) of the pigment dye prepared according" to Example 19 are added to 22,500 parts of. an aqueous viscose solution of 9% strength in a mixer. Thethus-colored spinning mass is stirred for 15 minutes, then deaerated, and thereupon subjected to. conventional spinning anddesulfurizing proc esses. The other pigment dyes of the invention may be similarly employed.

A lower alkyl 0 wherein 1 stands for a member selected from the group consisting of hydrogen, chlorine, bromine, methyl and SOsH, and w stands'for a member selected from the group consistingof chlorine, bromine and nitro, with an amine corresponding to the formula wherein R stands for a' member selected from the group consisting of hydrogen, alkyl and acyl, and R2 stands for a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, mononuclear aralkyl and mononu-' clear'he'te'ro cyclic"radicals.

2. The process for themanufacture of a compound of the aza(3)-benzanthrone series which comprises condens 'irig 1 carbethoxy 2 methyl 6 bromo aza(3) benzanthrone-4-sulfonic acid with ammonia in the presence of an acid-binding agent and in the absence of a l copper catalyst.

3. The process for the manufacture of acompound of v the aza(3)-benzanthrone series which comprises condensing 1 carbethoxy 2,4 dimethyl 6 bromo aza(3) benzanthrone with amylamine in the presence of an acidbinding agent and in the absence of a copper catalyst.

4. The process for the manufacture of a compound of the aza(3)benzanthrone series which comprises condensing 1 carbethoxy 2,4 dimethyl 6 bromo aza(3)-benzanthrone with1-aminobenzene-4-sulfoniciacid in the presence of an acid-binding agent and in the absence of a copper catalyst. v

5. The process for the manufacture of a compound of the aza(3)-benzanthrone series which comprises condensing 1 carbethoxy 2 methyl 4,6 dibromo aza(3)-benzanthrone with 1-amino-4-acetylaminobenzene in the presence of an acid-binding agent and in the absence of a copper catalyst.

6. The process for the manufacture of a compound of the aza(3)-benzanthrone series which comprises condensing 1 carbethoxy 2 methyl 4,6 dibromo aza(3)-benzanthrone with l-aminoanthraquinone in the presence of an acid-binding agent and in the absence of a copper catalyst.

7. A dye of the aza(3)-'benzanthrone series which corresponds to the formula (H) CH3 l 6 consisting of hydrogen, chlorine, bromine, methyl, lower alkoxy, mononuclear aryloxy and SOaH, Ristands for a member selected from the group consisting of hydrogen, alkyl and acyl, R2 stands for a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, mononuclear aralkyl and mononuclear heterocyclic radicals,,and n is one of the integers 1, 2, 3 and 4.

8. The compound of the formula 0 OH; aCaO-Hl SOLE ll 0 NH:

9. The compound of the formula O NH-CsHn 10. The compound of the formula CH1 I 11. The compound of the formula Tl H3 H502oo 6 N NHOOCH:

12.The compound of the formula References Cited in the file of this patent v M FOREIGN PATENTS 185,;548' Germany June 26, 1906 OTHER REFERENCES Anemia; J. Am. Chem. Soc., vol. '72, pp. 585-588 1950 

7. A DYE OF THE AZA(3)-BENZANTHRONE SERIES WHICH CORRESPONDS TO THE FORMULA 